The wondrous world

of carbon nanotubes

Final Presentation IFP 2

February 26, 2003
 IFP group 2
Group members:
• M.Daenen (N) • P.G.A.Janssen (ST)
• R. de Fouw (ST) • K. Schouteden (N)
• B. Hamers (ST) • M.A.J. Veld (ST)

Client:
• Prof. P.H.L. Notten (Philips / TU/e)
• ir. R.A.H. Niessen (Philips)

Tutor:
• X.E.E. Reynhout
 Overview
• Introduction
• Synthesis & Purification
• Overview of applications
• Single nanotube measurements
• Energy storage
• Molecular electronics
• Conclusion and future outlook
 Introduction: common facts
• Discovered in 1991 by Iijima
• Unique material properties
• Nearly one-dimensional structures
• Single- and multi-walled
 Introduction: nanotube structure
• Roll a graphene sheet in a certain direction:
• Armchair structure

• Zigzag structure

• Chiral structure

• Defects result in bends and transitions

 Introduction: special properties
• Difference in chemical reactivity for
end caps and side wall
• High axial mechanical strength
• Special electrical properties:
– Metallic
– Semi conducting
 Synthesis: growth mechanism
• Metal catalyst
• Tip growth / extrusion growth
 Synthesis: overview
• Commonly applied techniques:
– Chemical Vapor Deposition (CVD)
– Arc-Discharge
– Laser ablation

• Techniques differ in:

– Type of nanotubes (SWNT / MWNT / Aligned)
– Catalyst used
– Yield
– Purity
 Synthesis: CVD
•Gas phase deposition
•Large scale possible
•Relatively cheap

•SWNTs / MWNTs
•Aligned nanotubes
•Patterned substrates
 Synthesis: arc discharge
• MWNTs and SWNTs • Relatively cheap
• Batch process • Many side-products
 Synthesis: laser ablation
• Catalyst / no catalyst
• MWNTs / SWNTs
• Yield <70%

• Use of very strong laser

• Expensive (energy costs)
• Commonly applied
 Purification
• Contaminants:
– Catalyst particles
– Carbon clusters
– Smaller fullerenes: C60 / C70

• Impossibilities:
– Completely retain nanotube structure
– Single-step purification

• Only possible on very small scale:

– Isolation of either semi-conducting SWNTs
 Purification: techniques
• Removal of catalyst:
– Acidic treatment (+ sonication)
– Thermal oxidation
– Magnetic separation (Fe)

• Removal of small fullerenes

– Micro filtration
– Extraction with CS2

• Removal of other carbonaceous impurities

– Thermal oxidation
– Selective functionalisation of nanotubes
– Annealing
 Overview of potential
applications
< AFM Tip
> Molecular electronics
•Transistor

> FED devices:

•Displays < Others
• Composites
< Energy storage: • Biomedical
•Li-intercalation • Catalyst support
•Hydrogen storage • Conductive materials
•Supercaps • ???
 Overview of potential
applications
< AFM Tip
> Molecular electronics
•Transistor

> FED devices:

•Displays < Others
• Composites
< Energy storage: • Biomedical
•Li-intercalation • Catalyst support
•Hydrogen storage • Conductive materials
•Supercaps • ???
 Overview of potential
applications
< AFM Tip
> Molecular electronics
•Transistor

> FED devices:

•Displays < Others
• Composites
< Energy storage: • Biomedical
•Li-intercalation • Catalyst support
•Hydrogen storage • Conductive materials
•Supercaps • ???
 Energy Storage

Experiments & Modelling

• Electrochemical Storage of Lithium
• Electrochemical Storage of Hydrogen
• Gas Phase Intercalation of Hydrogen
• Supercapacitors
 Energy Storage
3-electrode cell
Work Electrode
reduction
CNT  xH 2O  xe -  oxidation
    CNT  xH +  xOH -

Counter Electrode
Ni  OH  2 
reduction
  NiOOH  H +
 e -
oxidation
Lithium Electrochemical Model
 Lithium Electro Chemical

•Equilibrium saturation
20 min
composition for graphite:
LiC6
10 min

•Purified SWNT bundles: 0 min

Li1.7C6

•Ball-milled SWNTs:
Li2.7C6
 Lithium Electro Chemical

Etching
•Two types: lengths of 4 and

Voltage [V]
0.5 μm
•Good Crev (Li2.1C6)
•Smaller hysteresis

Cut SWNTs have better

properties concerning Li
intercalation
Hydrogen Electrochemical
Lennard Jones Potential

  H-H 12   H-H 6 

U LJ  r   4 H-H     
 r   r  
Hydrogen Electrochemical
storage model

Model of Hydrogen Storage at

room temperature for different
diameters of SWNTs
Hydrogen Electrochemical
Charging & Discharging
Charge  Discharge Cycle
 Hydrogen Electrochemical

• Many contrasting conclusions:

– Positive Ranging from: 0.4 – 2.3 wt% H
– Negative: No systematic relationship
between purity and storage  storage not
due to SWNTs
• More investigations on the mechanism
of storage are needed in order to
explain this wide range of results
Gas Phase Intercalation of
Hydrogen model
 Gas Phase Intercalation of
Hydrogen

• Contrast in results is very high: range

from 0-67 wt%
• Reasonable range: 2-10 wt%
• More modelling needed
• To compare models they have to use
the same parameters
 Super Capacitor

Electrochemical double layer

E le c tr o d e ( + ) E le c tr o d e ( - )

S e p a ra to r
 Molecular electronics

• FEDs
•CNTFETs
•SETs
 Field Emitting Devices

Single Emitter

Film Emitter
 Field Emitting Devices

Single Emitter

Film Emitter
 Field Emitting Devices

Single Emitter

Film Emitter
 Patterned Film Field Emitters

•Etching and
lithography
•Conventional CVD
•Soft lithography
Transistor Principle in
CNTFETs

 Transistor

CNTFET 
Doping of CNTs
Single Electron transistor
 Conclusions
• Mass production is nowadays too expensive
• Many different techniques can be applied for
investigation
• Large scale purification is possible
• FEDs and CNTFETs have proven to work
and are understood
• Positioning of molecular electronics is difficult
• Energy storage is still doubtful, fundamental
investigations are needed